Water-insoluble oxyalkylated drastically oxidized castor oil and method of making same



Patented Nov. 16, 1943 t. l 2,334,390 UN TE S ATES OFFICE 1 2,3343% M WATER-INSOLUBLE OXYALKYLATED DRAS- TICALLY OXIDIZED CASTQR on, mp;

METHOD OF MAKING SAME;

Melvin De Groote,.University City; and Bernhard l ,Keiser, Webster,;- Groves, ,-Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del.,. a corporation of Delaware No Drawing. Original application July 7,: 1941, A I

' Serial No. 401,382; j. Divided, and thisapplica ,tion November 30, 1942, SeriaLNo. 467,474 I 5 Claims, T (c1. zen-40c) This invention-relates to-a'new chemical prod uctor compound and to the manufacture of:

same, our present applicationbeing a division of-our co-pendingapplication Serial No. 401,382,

temperature is*just slightly above the boiling point of water and when oxidation is withair atatmospheric "pressure.

Mild oxidationfire., voxidation as exemplified I byJthe exposure ofia' ofcastor oil to air, for an extendedperiod,ofttime, such as weeks, or

i even months (see, Chemical'lechnology and Analysis of Oils, Fats, and Waxes, by Lewkowitsch,

filed July 7, 1941, which subsequently matured as 5 sixth edition, volume 2, page406) produces rela- U. S. Patent No.'2,307,494, dated January 5,1943, tively smalljmodifications' of certain important 11 One object of our invention is to'provide a new indices,'such as the iodine value, the acetyl value, chemical product or compoundth'atisparticularand the saponifi'cation' value. If drastic oxidaly adapted for use as a demulsifier in theresolution takes place, eitherby continued mildoxidation of crude oil emulsions; tion, or by more vigorousoxidationfrom the very Another object is to provide a practicable methbeginning of the reaction, "as induced by either od for manufacturing said new chemical product a higher reaction temperature or the presence or co'mpound.- i i a V of a catalyst, then there is obtained an oxidized Although one of the primary objects of our oil having characteristics which clearly indicate invention is to provide a new compound oncom 15 that drastic oxidation. has taken place. These position of matter thatisan efficient demulsifier iridices of drastic oxidation are a relatively low for crude oil emulsions of the water-in-oil type, iodine value, .such as 70f or .less, and may be as the said compound or composition of matter may low as40, or thereabouts; a saponification value be employed in other arts, 'as hereinafter indie of 215 to 2 83, or-there an acetyl Value Of cated. It also may have additional uses in v'ariapproximately loo-200; an increased viscosity ous other fields which have not yet been investisuchthat the material may be hardly mobile at gated. ordinary temperatures; a specific gravity of al- Thecomposition of matter herein contemplate most one, or a trifle over one at m an ed, and particularly for use as ademulsifier, ,is creased refractiveindex; an in the absence of obtained by the oxyalkylation of blown or, oxiother colorin m r,- YellOWFtO 1 Orange dized castor oil to a point definitely short of color. The color at times may be a questionable water-solubility. 1 1 index, since some oxidized oastor oils are bleached It js well known thatoxidized oils canbe obs. to make them particularly adaptable foruseas tained from castor oil ricinoleic acid and various plasticizers in 1ight1001'0red IeSiHOid b d S- derivatives of ricinoleic acid,.such "Mo o- Drastically oxidize'd castor oil can be prepared ricinolein, diricinolein' and polyricinoleic acids. by Well known methods, or such products can They are produced by the common practice :of be' p r has d in th op n market under various blowing or oxidizing castor oil andcsimilar fatty trade names, a b as l nd d oils or acids, particularly non-drying unsaturated castor oil, blended bodied Castor P s d fatty oils,.by means of a gaseous mediumysuch Cast l, "OXidiZEd L y iiastor as air, oxygen, ozone, or ozoniaed air. The .gaseoil, f Q These Various ous medium, such as air, may be moist or dry and trade-names app be pplied to drasticallythe oxidation may take place in the presence or oxidizedcastor oils which differ me ely in e absence of a catalyst. The catalyst may belof a but notin 'kind. i i i metallic, type, such. as lead ricinoleate, .cobalt 40 The color of these oils is still pale or light colricinoleate, manganese ricinoleate, etc.; oriitmay cred in comp it h 011 from Which y be of the organic type which produces peroxide; havebeen derived. Usually,they are fairly transsuch as alpha pinene, linseed oil, etc. Oxidation 1 par P ly reasonably thin layers, for may take place at atmospheric pressure or superinstance, an 1 inchor less; s ch 5 represent atmospheric pressure, i."e., pressures up to or greatenorlesserdgree'sof partial oxidation in includingzoo pounds gauge pressure, and at any the n ethat thereis a 'drasticchan in om-- temperature slightly above the boiling point of par s nw t Change -D When water, fOninstance, 120*"C.,upto any temperature afilm ofcastoroil isexpo's'ed to air. g which does not :produce undue decomposition 5o For'thesake of diifere'ntiation, oils of'the kind by pyrolyticreaction. w previously described will be referred to as pale The time of blowing may be fairly briefjfor blown, drastically-o idized 'castor oils; and the example, 8-10 hours; or it may bequite extensive, same terminology is intended to apply to all other for-instance, as longas 10-12-14 days, the longer ricinoleio bodies of the kindhereinafter detime periods being employed generally when the scribed: In addition to pale blown drasticallyoxidizedcastor oil, there is also another type of the' kind described in U. SJPatent No.-2,023,979,- to Stehr, December '10, 1935. The'product describedin said Stehrpatent is characterized by the fact that, drastic oxidation is continued past the stage where a pale blown oil is obtained and where/as a matter of fact, a super oxidized product of almost semi-livery consistency is obtained.

Such products are usually much darker in color than the pale blown castor oils, for the reason that certain side reactions occur with l the formation of dark colored by-products; and as a result, the transparencyof the oil has greatly decreased or disappeared, and it 'is apt to be opaque in nature.

Attention is directed particularly to U. S. Patent No. 2,183,487, dated December .12, 1939, ;.to

Colbeth, to the extent that it discloses details.

as to the oxidation of castor oil in a manner that is particularly desirable.

Our preference is to subject a pale blown castor oil of the following characteristics, to oxyalkylation, particularly oxyethylation:

Acid number 15.1 to 25.0 Saponification number 230.5 to 274.0

It is well known that if triricinolein, preferably as ademulsifier, and also has utilityin arts where blown castor oil is sometimes employed, as, for example, as a plasticizer in the manufacture of .various plastics; as an ingredient in furniture polish, etc.

In the manufacture of such oxyalkylated blown .castor oils, we prefer, for the sake of convenience, to consider the molecular weight of the =blown castor oil the same as if it were unmodified triricinolein. but 'it is convenient, thus subsequent reference This is not strictly correct,

' to one pound mole of blown castor oil is intended to mean 944 lbs. Our preference is to treat one ,pound mole of castor oil with approximately in the form of castor oil, is treated with an oxyalkylating agent, particularly ethylene oxide, propylene oxide, butylene oxide, glycidol, or the like, and if one employs a large molecular proportion of the oxyalkylating agent for each mole can convert castor oil into a water-soluble product. The conventional procedure is well known, and generally speaking, involves nothing more nor less than heating castor oil in the presence or the like, under comparatively low pressures and fairly low temperatures, and usually in the presence of an alkylene catalyst, as, for example, sodium ricinoleate. The temperatures employed are generally above. 100- C, and below 20.0? C. The pressures employed are generally above 100 lbs. gauge and below 390 lbs. gauge pressure. Sometimes oxyalkylation is conducted ina-continuous manner by introduction of the ethylene oxide in. a gaseous state. quently, and most conveniently, the oxide is introduced in .a liquid form, in a, comparatively small amount, for instance, 300 lbs. of castor oil and 30 lbs. of ethylene oxide, along with ap-.

More fre- 1 proximately one pound of sodium ricinoleate.

Reaction is allowed to take place under pressure inthe manner above described until all the ethylene oxide is absorbed. Another portion of ethylene oxide is added, and the; procedure repeated until water solubility is obtained, Not infrequent vas many as 30 lbs. moles of the oxyalkylating agent are employed for one pound mole of triricinolein, in order to obtain complete water sp u il ed e s to ari t ene xide pr motes solubility in lower molecularproportions than propylene oxide or butylene oxide. Furthermore, ethyleneoxide is preferable, due to its greater reactivity.

We have foundthat if one-oxyalkylates blown or oxidized castor oil with any of the usual; 0xy-.

alkvlatin j age s ndic ed. a cula y ethy ne o t a p nt sh rt of water'solubi itv. one obtai s apro uct. wh ch has part cular mer t oxide are employed. of successive small amounts of alkylene oxide 1 the kind intended to sweeten gasoline.

three, six, or nine moles of ethylene oxide. Drastic oxyethylation may introduce as many as 18 or 20moles of ethylene oxide, Without yielding a water-soluble product. In the event propylene oxide .or butylene oxide is employed, a greater molar ratio of the alkylene oxide can be employed, but greater difficulty is incurred, because such reactants combine less readily than ethylene oxide. It is to be noted that we are concerned with oxyalkylation to a degree short of water solubility.

Composition of matter, Example 1 One pound mole of pale blown castor oil of the kind described by the above table is reacted with three pound moles of ethylene oxide, in the presence of of 1% of sodium stearate-as a cata y t v Composition of matter, Example 2 Same procedure is followed as in Example 1, preceding, except that 6 pound moles of ethylene or occurrence of the ricinoleyl radical, that one I oxide are employed C'o mposition of matter, Example 3:

Same procedure is followed as in Example 1, preceding, except that 9 pound moles of ethylene We have found that the particular chemical compounds or reagents 'herein' described, and particularly desirable for use. as demulsifiers, may also be used for other purposes, for instance, as a break inducer in doctor treatment of Other uses include employment as -a component of furniture polishes, and as a plasticizer in resin manufacture.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

.1. A new composition of matter consisting of a water-insoluble. oxyalkylated drastically-oxidized castor oil.

'2. A new composition of matter consisting of a waterinsoluble .oxyethylated drastically-oxidized castor oil.

3. A new composition of matter consisting of a. water-insoluble oxyethylated drastically-oxidized paleblown castor oil.

4. A newcomposition of matter consisting of a: water-insoluble oxyethylated. drastically-oxidized castor oil of the .pale' blown type;v the oxyalkylation' of said castor, oil involving at least three and not more than nine. molesof ethylene oxide for each mole of triricinolein employed prior to oxidation.

7 5. Inthe manufacture of a, composition of matter as defined in claim 1, the step of oxyalkylating a drastically-oxidized castor oil to; a point short ofwater solubility.

MELVIN DE. GROOTE." BERNHARD KEISER. I 

